US5015770A - Process for preparing (hydrocarbylthio) aromatic amines - Google Patents
Process for preparing (hydrocarbylthio) aromatic amines Download PDFInfo
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- US5015770A US5015770A US07/552,892 US55289290A US5015770A US 5015770 A US5015770 A US 5015770A US 55289290 A US55289290 A US 55289290A US 5015770 A US5015770 A US 5015770A
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- Prior art keywords
- iodine
- aniline
- disulfide
- hydrocarbylthio
- dimethylaniline
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- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- -1 hydrocarbyl disulfide Chemical compound 0.000 claims abstract description 17
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 6
- OIVUHPTVQVCONM-UHFFFAOYSA-N 6-bromo-4-methyl-1h-indazole Chemical compound CC1=CC(Br)=CC2=C1C=NN2 OIVUHPTVQVCONM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical group CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 20
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 17
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical group CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 16
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000011968 lewis acid catalyst Substances 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims 4
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 claims 2
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 description 2
- CUKYBSIUPGLCRU-UHFFFAOYSA-N 4-methyl-2-methylsulfanylbenzene-1,3-diamine Chemical compound CSC1=C(N)C=CC(C)=C1N CUKYBSIUPGLCRU-UHFFFAOYSA-N 0.000 description 2
- PXKDTKGHGSOJNQ-UHFFFAOYSA-N 4-methyl-n,n-bis(methylsulfanyl)aniline Chemical compound CSN(SC)C1=CC=C(C)C=C1 PXKDTKGHGSOJNQ-UHFFFAOYSA-N 0.000 description 2
- MOYGVRJWENHCRI-UHFFFAOYSA-N 4-methyl-n-methylsulfanylaniline Chemical compound CSNC1=CC=C(C)C=C1 MOYGVRJWENHCRI-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- CTWQGTOWGFCWNW-UHFFFAOYSA-N 1,3-dimethylpyrrole Chemical compound CC=1C=CN(C)C=1 CTWQGTOWGFCWNW-UHFFFAOYSA-N 0.000 description 1
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- TZOVOULUMXXLOJ-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)disulfanyl]benzene Chemical class C1=CC(C)=CC=C1SSC1=CC=C(C)C=C1 TZOVOULUMXXLOJ-UHFFFAOYSA-N 0.000 description 1
- JVAHNNNQPJDOHQ-UHFFFAOYSA-N 2,4-dimethyl-n-methylsulfanylaniline Chemical compound CSNC1=CC=C(C)C=C1C JVAHNNNQPJDOHQ-UHFFFAOYSA-N 0.000 description 1
- 150000005000 2,6-diaminotoluenes Chemical class 0.000 description 1
- WDFWZGUOMCIPCI-UHFFFAOYSA-N 2,6-dimethyl-4-methylsulfanylaniline Chemical compound CSC1=CC(C)=C(N)C(C)=C1 WDFWZGUOMCIPCI-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- KZXDETHBUVFJMZ-UHFFFAOYSA-N 2-ethylbenzene-1,3-diamine Chemical compound CCC1=C(N)C=CC=C1N KZXDETHBUVFJMZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- SBWHGZIKDZAXSD-UHFFFAOYSA-N 4-chloroaniline;4-phenylsulfanylaniline Chemical compound NC1=CC=C(Cl)C=C1.C1=CC(N)=CC=C1SC1=CC=CC=C1 SBWHGZIKDZAXSD-UHFFFAOYSA-N 0.000 description 1
- WOYZXEVUWXQVNV-UHFFFAOYSA-N 4-phenoxyaniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1 WOYZXEVUWXQVNV-UHFFFAOYSA-N 0.000 description 1
- KGWPHCDTOLQQEP-UHFFFAOYSA-N 7-methylindole Chemical compound CC1=CC=CC2=C1NC=C2 KGWPHCDTOLQQEP-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
- C07B45/06—Formation or introduction of functional groups containing sulfur of mercapto or sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
Definitions
- This invention relates to (hydrocarbylthio)aromatic amines and more particularly to a process for preparing them.
- An object of this invention is to provide a novel process for preparing (hydrocarbylthio)aromatic amines.
- Another object is to provide such a process wherein the reaction rates and/or yields of mono(hydrocarbylthio)aromatic amine products are improved.
- a further object is to provide such a process using a recyclable catalyst.
- Aromatic amines utilizable in the practice of the invention include (1) compounds having at least one amino group attached to a carbocyclic or heterocyclic ring of an unbridged aromatic compound, such as a benzene, naphthalene, anthracene, pyrrole, pyridine, or indole compound, and (2) reactive heterocyclic amines, such as pyrrole, indole, imidazole, etc.
- the compounds may bear no substituents other than the required amino group, or they may bear substituents inert to the reaction conditions, such as one or more additional amino groups or substituents such as chloro, fluoro, alkyl, alkoxy, alkylthio aryl, aryloxy, arylthio, alkaryl) or aralkyl groups on any positions other than those to be substituted by hydrocarbylthio groups.
- Useful aromatic amines include, e.g., 1,3-dimethylpyrrole, 1-methylpyrrole, 7-methylindole, aminobenzenes containing one or two amino groups, such as aniline, 3-methylaniline, 4-methylaniline, 2,4- and 2,6-dimethylanilines, 4-chloroaniline 4-(phenylthio)aniline, 4-phenoxyaniline, 2-ethylaniline, N-methylaniline, 2,4- and 2,6-diaminotoluenes, 2,6-diamino-1-ethylbenzene, etc.
- the preferred amines are the aminobenzenes.
- Bridged aromatic amines such as 4,4'-methylenedianiline, etc., have not been successfully employed in the practice of the invention.
- Hydrocarbyl disulfides which may be reacted with the aromatic amines include saturated and unsaturated aliphatic, cycloaliphatic, and aromatic disulfides, such as methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, allyl, cyclopentyl, cyclohexyl, phenyl, benzyl, and p-tolyl disulfides, etc.
- This component of the reaction mixture is generally employed in at least the stoichiometric amount required to yield the desired (hydrocarbylthio)aromatic amine and is preferably employed in an excess which permits the maximum achievable reaction rate.
- the amount of hydrocarbyl disulfide used is about 1-3, preferably 2-3 mols per mol of aromatic amine.
- the reaction of the aromatic amine with the hydrocarbyl disulfide is generally conducted at a temperature in the range of about 20°-300° C., preferably about 100°-200° C., and at a pressure of atmospheric up to about 350 kPa; and, as mentioned above, it is conducted in the presence of iodine, iodine monochloride, or iodine monobromide (preferably iodine) as the sole catalyst.
- the catalyst is employed in catalytic amounts, generally in a catalyst/aromatic amine mol ratio of about 0.01-0.5/1, preferably about 0.01-0.2/1.
- the process of the invention like the processes of Ranken et al.-I and -II and Davis-I and -II, results in the formation of (hydrocarbylthio)aromatic amines which are useful as intermediates in the preparation of biologically-active materials, polyurethanes, etc. It is particularly advantageous in that (1) it is characterized by higher reaction rates and/or higher yields of mono(hydrocarbylthio)aromatic amines than are obtained when other Lewis acid catalysts are employed and (2) it uses a catalyst which can be recycled.
- a suitable reaction vessel was charged with 25 g of 4-methylaniline and 5 g of aluminum chloride, flushed with nitrogen, and heated to 170° C. Then 22 mL of dimethyldisulfide was added slowly over a 21-hour period while the temperature was maintained at 130°-142° C. The product was then dumped all at once into water whereupon the 4-methylaniline solidified. The product was extracted with toluene and the organic layer analyzed by GC. Analysis showed that the reaction resulted in only 14% conversion of the 4-methylaniline to mono(methylthio)-4-methylaniline and no co-formation of di(methylthio)4-methylaniline.
- a suitable reaction vessel was charged with 20 g or 4-methylaniline and 1.1 g of iodine, flushed with nitrogen, and heated to 148° C. Then 20 mL of dimethyldisulfide was added slowly over five hours while maintaining a temperature of 140°-150° C. The mixture was heated for a total of 21 hours. Analysis showed the following conversions of 4-methylaniline to mono-(methylthio)-4-methylaniline and di(methylthio)-4-methylaniline:
- Example II was repeated except that 21.3 g of 2,6-dimethylaniline was substituted for the 2,4-dimethylaniline and the total heating time was 25.5 hours. Analysis showed the following conversions of 2,6-dimethylaniline to mono(methylthio)-2,6-dimethylaniline (MM-2,6-DMA):
- Example III The product of Example III was distilled to purify the product and recover the catalyst residue.
- the 4.8 g of purple residue was dissolved in 25 g of 2,6-dimethylaniline, after which the solution was charged to a suitable reaction vessel which was then flushed with nitrogen and heated.
- Dimethyldisulfide (19.5 mL) was added over a period of two hours while maintaining the temperature at 140°-150° C., and heating was continued for a total of 17 hours. Analysis showed the following conversions of 2,6-dimethylaniline to MM-2,6-DMA:
- a suitable reaction vessel was charged with 20 g of 2,4-diaminotoluene and 1 g of iodine and heated to 130°-150° C. under nitrogen, after which 17 mL of dimethyldisulfide was added over period of 5.5 hours. After the 5.5 hours analysis showed that the reaction resulted in the conversion of 23.5% of the 2,4-diaminotoluene to mono(methylthio)-2,4-diaminotoluene and 1.5% conversion to di(methylthio)-2,4-diaminotoluene.
- Example VI and Comparative Example B demonstrate that, in the hydrocarbylthiation of aromatic diamines, iodine is a better catalyst than cuprous iodide when a mono(hydrocarbylthio) product is desired, while cuprous iodide is a better catalyst than iodine when a di(hydrocarbylthio) product is desired.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(Hydrocarbylthio)aromatic amines are prepared by reacting an aromatic amine, such as an aminobenzene, with a hydrocarbyl disulfide, such as an alkyl disulfide, in the presence of iodine, iodine monochloride, or iodine monobromide as a catalyst.
Description
This application is a continuation of application Ser. No. 452,693, filed Dec. 18, 1989, now abandoned, which is a continuation of application Ser. No. 254,857, filed Oct. 7, 1988, now abandoned.
This invention relates to (hydrocarbylthio)aromatic amines and more particularly to a process for preparing them.
As disclosed in U.S. Pat. No. 4,594,453 (Ranken et al.-I), it is known that various (hydrocarbylthio)aromatic amines are useful as intermediates in the preparation of biologically-active materials, polyurethanes, etc.; and they can be prepared by reacting an aromatic amine with a hydrocarbyl disulfide in the presence of a catalytic amount of a Lewis acid. The preferred catalysts of Ranken et al.-I are metal halides, such as aluminum chloride, boron trifluoride, boron trichloride, ferric chloride, and zinc chloride.
In the case of at least some aromatic amines, it has been found that the preferred catalysts identified by Ranken et al.-I have the disadvantages of effecting the desired hydrocarbylthiations at too slow a rate to be completely satisfactory and of sometimes providing too low a yield of product. These disadvantages can frequently be overcome by the use of the hydrogen iodide, ammonium iodide, and cuprous iodide catalysts of U.S. Pat. No. 4,670,597 (Ranken et al.-II), the metal iodide and bromide catalysts of U.S. Pat. No. 4,670,598 (Davis-I), or the iodine-promoted metal and metal halide catalysts of U.S. Pat. No. 4,751,330 (Davis-II). However, there is still a need for improvement in the reaction rates and/or yields of mono(hydrocarbylthio)-aromatic amines in the hydrocarbylthiation processes, and it would also be desirable to use a catalyst which could be recycled.
An object of this invention is to provide a novel process for preparing (hydrocarbylthio)aromatic amines.
Another object is to provide such a process wherein the reaction rates and/or yields of mono(hydrocarbylthio)aromatic amine products are improved.
A further object is to provide such a process using a recyclable catalyst.
These an other objects are attained by reacting an unbridged aromatic amine with a hydrocarbyl disulfide in the presence of iodine, iodine monochloride, or iodine monobromide as the sole catalyst.
Aromatic amines utilizable in the practice of the invention include (1) compounds having at least one amino group attached to a carbocyclic or heterocyclic ring of an unbridged aromatic compound, such as a benzene, naphthalene, anthracene, pyrrole, pyridine, or indole compound, and (2) reactive heterocyclic amines, such as pyrrole, indole, imidazole, etc.
The compounds may bear no substituents other than the required amino group, or they may bear substituents inert to the reaction conditions, such as one or more additional amino groups or substituents such as chloro, fluoro, alkyl, alkoxy, alkylthio aryl, aryloxy, arylthio, alkaryl) or aralkyl groups on any positions other than those to be substituted by hydrocarbylthio groups.
Useful aromatic amines include, e.g., 1,3-dimethylpyrrole, 1-methylpyrrole, 7-methylindole, aminobenzenes containing one or two amino groups, such as aniline, 3-methylaniline, 4-methylaniline, 2,4- and 2,6-dimethylanilines, 4-chloroaniline 4-(phenylthio)aniline, 4-phenoxyaniline, 2-ethylaniline, N-methylaniline, 2,4- and 2,6-diaminotoluenes, 2,6-diamino-1-ethylbenzene, etc. The preferred amines are the aminobenzenes.
Bridged aromatic amines, such as 4,4'-methylenedianiline, etc., have not been successfully employed in the practice of the invention.
Hydrocarbyl disulfides which may be reacted with the aromatic amines include saturated and unsaturated aliphatic, cycloaliphatic, and aromatic disulfides, such as methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, allyl, cyclopentyl, cyclohexyl, phenyl, benzyl, and p-tolyl disulfides, etc. This component of the reaction mixture is generally employed in at least the stoichiometric amount required to yield the desired (hydrocarbylthio)aromatic amine and is preferably employed in an excess which permits the maximum achievable reaction rate. Most commonly, the amount of hydrocarbyl disulfide used is about 1-3, preferably 2-3 mols per mol of aromatic amine.
The reaction of the aromatic amine with the hydrocarbyl disulfide is generally conducted at a temperature in the range of about 20°-300° C., preferably about 100°-200° C., and at a pressure of atmospheric up to about 350 kPa; and, as mentioned above, it is conducted in the presence of iodine, iodine monochloride, or iodine monobromide (preferably iodine) as the sole catalyst. The catalyst is employed in catalytic amounts, generally in a catalyst/aromatic amine mol ratio of about 0.01-0.5/1, preferably about 0.01-0.2/1.
In conducting the process of the invention, it is frequently preferred to (1) heat a mixture of the catalyst and aromatic amine at a suitable temperature, usually a temperature higher than the boiling point of the disulfide to be added, e.g. about 100°-250° C., until all of the catalyst has reacted and then (2) heat the reaction mixture at reflux temperature after the disulfide has been added to effect a hydrocarbylthiation process while removing evolved hydrocarbyl thiol by-product from the reaction vessel. However, it is also satisfactory to conduct the process by simply mixing the catalyst and reactants together and heating them to the reflux temperature. An inert solvent may be employed if desired but is unnecessary.
The process of the invention, like the processes of Ranken et al.-I and -II and Davis-I and -II, results in the formation of (hydrocarbylthio)aromatic amines which are useful as intermediates in the preparation of biologically-active materials, polyurethanes, etc. It is particularly advantageous in that (1) it is characterized by higher reaction rates and/or higher yields of mono(hydrocarbylthio)aromatic amines than are obtained when other Lewis acid catalysts are employed and (2) it uses a catalyst which can be recycled.
The following examples are given to illustrate the invention and are not intended as a limitation thereof.
A suitable reaction vessel was charged with 25 g of 4-methylaniline and 5 g of aluminum chloride, flushed with nitrogen, and heated to 170° C. Then 22 mL of dimethyldisulfide was added slowly over a 21-hour period while the temperature was maintained at 130°-142° C. The product was then dumped all at once into water whereupon the 4-methylaniline solidified. The product was extracted with toluene and the organic layer analyzed by GC. Analysis showed that the reaction resulted in only 14% conversion of the 4-methylaniline to mono(methylthio)-4-methylaniline and no co-formation of di(methylthio)4-methylaniline.
A suitable reaction vessel was charged with 20 g or 4-methylaniline and 1.1 g of iodine, flushed with nitrogen, and heated to 148° C. Then 20 mL of dimethyldisulfide was added slowly over five hours while maintaining a temperature of 140°-150° C. The mixture was heated for a total of 21 hours. Analysis showed the following conversions of 4-methylaniline to mono-(methylthio)-4-methylaniline and di(methylthio)-4-methylaniline:
______________________________________ Hours Mono (%) Di (%) ______________________________________ 5 23.5 0.5 21 62.8 6.2 ______________________________________
A suitable reaction vessel was charged with 20.1 g of 2,4-dimethylaniline and 1.8 g of iodine, flushed with nitrogen, and heated to 144° C. Then 15 mL of dimethyldisulfide was added over six hours at 140°-150° C., and heating was continued for a total of 23 hours. Analysis showed the following conversions of 2,4-dimethylaniline to mono(methylthio)-2,4-dimethylaniline (MM-2,4-DMA):
______________________________________ Hours MM-2,4-DMA (%) ______________________________________ 1.5 14 6 36 23 63 ______________________________________
Example II was repeated except that 21.3 g of 2,6-dimethylaniline was substituted for the 2,4-dimethylaniline and the total heating time was 25.5 hours. Analysis showed the following conversions of 2,6-dimethylaniline to mono(methylthio)-2,6-dimethylaniline (MM-2,6-DMA):
______________________________________ Hours MM-2,6-DMA (%) ______________________________________ 0.5 24 6 670 25.5 90 ______________________________________
The product of Example III was distilled to purify the product and recover the catalyst residue. The 4.8 g of purple residue was dissolved in 25 g of 2,6-dimethylaniline, after which the solution was charged to a suitable reaction vessel which was then flushed with nitrogen and heated. Dimethyldisulfide (19.5 mL) was added over a period of two hours while maintaining the temperature at 140°-150° C., and heating was continued for a total of 17 hours. Analysis showed the following conversions of 2,6-dimethylaniline to MM-2,6-DMA:
______________________________________ Hours MM-2,6-DMA (%) ______________________________________ 1 19 2 33 17 78 ______________________________________
A suitable reaction vessel was charged with 20.4 g of 2,6-dimethylaniline and flushed with nitrogen, after which 0.7 mL of iodine monochloride was added. The mixture was then heated to 140°-150° C. and 26 mL of dimethyldisulfide was added over a period of 26 hours. Analysis showed the following conversions of 2,6-dimethylaniline to MM-2,6-DMA:
______________________________________ Hours MM-2,6-DMA (%) ______________________________________ 1 19 2 38 6 66 25 93 ______________________________________
A suitable reaction vessel was charged with 20 g of 2,4-diaminotoluene and 1 g of iodine and heated to 130°-150° C. under nitrogen, after which 17 mL of dimethyldisulfide was added over period of 5.5 hours. After the 5.5 hours analysis showed that the reaction resulted in the conversion of 23.5% of the 2,4-diaminotoluene to mono(methylthio)-2,4-diaminotoluene and 1.5% conversion to di(methylthio)-2,4-diaminotoluene.
A suitable reaction vessel was charged with 20 g of 2,4-diaminotoluene and 1.3 g of cuprous iodide and heated to 130°-150° C. under nitrogen, after which 34 mL of dimethyldisulfide was added over a period of 6.7 hours. Analysis showed the following conversions of 2,4-diaminotoluene to mono(methylthio)-2,4-diaminotoluene and di(methylthio)-2,4-diaminotoluene:
______________________________________ Hours Mono (%) Di (%) ______________________________________ 1 54.9 12.1 2.5 39.1 53.9 3 31.7 64.3 3.5 21.6 76.4 4.7 11.9 87.1 6.7 3.0 96.0 ______________________________________
Example VI and Comparative Example B demonstrate that, in the hydrocarbylthiation of aromatic diamines, iodine is a better catalyst than cuprous iodide when a mono(hydrocarbylthio) product is desired, while cuprous iodide is a better catalyst than iodine when a di(hydrocarbylthio) product is desired.
It is obvious that many variations may be made in the products and processes set forth above without departing from the spirit and scope of this invention.
Claims (18)
1. In a process for reacting an unbridged aromatic amine with a hydrocarbyl disulfide in the presence of a Lewis acid catalyst to form a (hydrocarbylthio)aromatic amine, the improvement which comprises conducting the reaction in the presence of iodine, or iodine monobromide as the Lewis acid.
2. The process of claim 1 wherein the catalyst is iodine.
3. In a process for reacting compounds having at least one amino group attached to a carbocyclic or heterocyclic ring of an unbridged aromatic compound with a hydrocarbyl disulfide in the presence of a Lewis acid catalyst to form a mono-hydrocarbylthio) aromatic amine, the improvements comprising conducting the reaction in the presence of a catalytic amount of iodine or iodine monobromide as the Lewis acid.
4. The process of claim 3 wherein the aromatic amine is an aminobenzene.
5. The process of claim 4 wherein the aminobenzene is an aniline.
6. The process of claim 5 wherein the aniline is 4-methylaniline.
7. The process of claim 5 wherein the aniline is 2,4-dimethylaniline.
8. The process of claim 5 wherein the aniline is 2,6-dimethylaniline.
9. The process of claim 4 wherein the aminobenzene is a diaminobenzene.
10. The process of claim 9 wherein the diaminobenzene is a diaminotoluene.
11. The process of claim 3 wherein the hydrocarbyl disulfide is an alkyl disulfide.
12. The process of claim 11 wherein the alkyl disulfide is methyl disulfide.
13. The process of claim 3 wherein an aniline is reacted with methyl disulfide in the presence of iodine.
14. The process of claim 13 wherein the aniline is 4-methylaniline.
15. The process of claim 13 wherein the aniline is 2,4-dimethylaniline.
16. The process of claim 13 wherein the aniline is 2,6-dimethylaniline.
17. The process of claim 3 wherein a diaminobenzene is reacted with methyl disulfide in the presence of iodine.
18. The process of claim 17 wherein the diaminobenzene is a diaminotoluene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117304080A (en) * | 2023-11-21 | 2023-12-29 | 东营海瑞宝新材料有限公司 | Production process of dimethyl thiotoluene diamine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3943161A (en) * | 1973-11-27 | 1976-03-09 | Toyo Soda Manufacturing Co., Ltd. | Process for producing conjugated dienes containing a cyano group |
| US4594453A (en) * | 1984-06-11 | 1986-06-10 | Ethyl Corporation | Process for preparing (hydrocarbylthio)aromatic amines |
| US4751330A (en) * | 1985-11-08 | 1988-06-14 | Ethyl Corporation | Process for preparing (hydrocarbylthio) aromatic amines |
-
1990
- 1990-07-16 US US07/552,892 patent/US5015770A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3943161A (en) * | 1973-11-27 | 1976-03-09 | Toyo Soda Manufacturing Co., Ltd. | Process for producing conjugated dienes containing a cyano group |
| US4594453A (en) * | 1984-06-11 | 1986-06-10 | Ethyl Corporation | Process for preparing (hydrocarbylthio)aromatic amines |
| US4751330A (en) * | 1985-11-08 | 1988-06-14 | Ethyl Corporation | Process for preparing (hydrocarbylthio) aromatic amines |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117304080A (en) * | 2023-11-21 | 2023-12-29 | 东营海瑞宝新材料有限公司 | Production process of dimethyl thiotoluene diamine |
| CN117304080B (en) * | 2023-11-21 | 2024-02-02 | 东营海瑞宝新材料有限公司 | Production process of dimethyl thiotoluene diamine |
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